Synthesis, structures and electrochemical properties of hydroxyl- and pyridyl-functionalized diiron azadithiolate complexes

The hydroxyl- and pyridyl-functionalized diiron azadithiolate complexes [{(μ-SCH2)2N(CH2CH2OH)}Fe2(CO)6] (1) and [{(μ-SCH2)2N(CH2CH2OOCPy)}Fe2(CO)6] (Py = pyridyl) (2) were prepared as biomimetic models of the active site of Fe-only hydrogenases. Both complexes were characterized by MS, IR, 1H NMR spectra and elemental analysis. The molecular structures of 1 and 2 were determined by single crystal X-ray analysis. A network is constructed by intermolecular H-bonds in the crystals of 1. An S⋯O intermolecular contact was found in the crystals of 2, which is scarcely found for organometallic complexes. Cyclic voltammograms of 1 and 2 were studied to evaluate their redox properties.

Graphical abstractHydroxyl- and pyridyl-functionalized diiron azadithiolate complexes, [{(μ-SCH2)2N(CH2CH2OH)}Fe2(CO)6] (1) and [{(μ-SCH2)2N(CH2CH2OOCPy)}Fe2(CO)6] (2), were prepared and crystallographically characterized as biomimetic models of the Fe-only hydrogenase active site. A network is constructed by intermolecular H-bonds in the crystals of 1. An S⋯O intermolecular contact was found in the crystals of 2.Figure optionsDownload full-size imageDownload as PowerPoint slide